Comonomer pretreated bimetallic catalyst for blow molding and film applications

Abstract

The invention relates to a catalyst component which is a tract product of reagents comprising silica which has a pore volume which exceeds 2.9 cc/gram and an average pore diameter which exceed 400 Angstroms; a metallocene of a first transition metal, activated by an alumoxane, a contact product of dialkylmagnesium and trialkylsilanol, a second transition metal source which exhibits a hydrogen response which is different from that of the metallocene an olefin of 4 to 20 carbon atoms. This catalyst component is activated by an aluminum alkyl activator.

What is claimed is: 
     
       1. A catalyst component made by a process comprising providing silica having an hydroxyl content of at least 0.7 millimoles per gram of silica;   impregnating the silica with a solution of activated metallocene complex, to form a particulate product which contains OH groups pendant from silica;   contacting a slurry of the particulate product with a reaction product of trihydrocarbyl silanol and dialkylmagnesium, and allowing the OH groups pendant from silica and the reaction product to form a contact product;   impregnating the contact product with a second transition metal source which exhibits a different hydrogen response from the metallocene complex to form a solid; and   reacting said solid with an olefin of 4 to 20 carbon atoms.   
     
     
       2. The catalyst component of claim 1 wherein the silica is calcined at 200-300 degrees C. 
     
     
       3. The catalyst component of claim 1 wherein the reaction product is formed by a 1:1 molar ratio of silanol and dialkylmagnesium to form a product. 
     
     
       4. The catalyst component of claim 1, wherein the dialkylmagnesium is dibutylmagnesium and the trihydrocarbyl silanol is triethylsilanol and the reaction product comprises Et 3  SiOMgBu and BuH where Et is ethyl and Bu is butyl. 
     
     
       5. The catalyst component of claim 1, wherein the silica has a pore volume which exceeds 2.9 cc/gram. 
     
     
       6. The catalyst component of claim 1, wherein the second source of transition metal is a contact product of titanium tetrachloride and an alcohol containing 1 to 10 carbon atoms. 
     
     
       7. The catalyst component of claim 1, wherein the olefin comprises hexene. 
     
     
       8. The catalyst component of claim 1 wherein the metallocene is 1,1-ethylene-bis(indenyl)zirconium dichloride. 
     
     
       9. A supported catalyst comprising an alkyl aluminum compound selected from the group consisting of trialkylaluminum and dialkylaluminum hydride, and a catalyst component of claim 1. 
     
     
       10. The catalyst component of claim 9, wherein the silica is calcined at 200-300 degrees C. 
     
     
       11. The catalyst component of claim 9, wherein the reaction product is formed by a 1:1 molar ratio of silanol and dialkylmagnesium to form a product. 
     
     
       12. The catalyst component of claim 9, wherein the silica has a pore volume which exceeds 2.9 cc/gram. 
     
     
       13. The catalyst composition of claim 6, wherein the silica contains hydroxyl group of greater than 0.7 millimoles per gram silica. 
     
     
       14. The catalyst component of claim 6, wherein the second source of transition metal is a contact product of titanium tetrachloride and an alcohol containing 1 to 10 carbon atoms. 
     
     
       15. The catalyst component of claim 6, wherein the olefin comprises hexene. 
     
     
       16. The catalyst component of claim 6, wherein the alcohol is pentanol. 
     
     
       17. The catalyst component of claim 6, wherein the metallocene is 1,1-ethylene-bis(indenyl)zirconium dichloride.